EP0941384A1 - Stärkederivat enthaltende kolophoniumemulsion zur papierleimung - Google Patents

Stärkederivat enthaltende kolophoniumemulsion zur papierleimung

Info

Publication number
EP0941384A1
EP0941384A1 EP97947760A EP97947760A EP0941384A1 EP 0941384 A1 EP0941384 A1 EP 0941384A1 EP 97947760 A EP97947760 A EP 97947760A EP 97947760 A EP97947760 A EP 97947760A EP 0941384 A1 EP0941384 A1 EP 0941384A1
Authority
EP
European Patent Office
Prior art keywords
composition
rosin
paper
derivative
starch derivative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97947760A
Other languages
English (en)
French (fr)
Other versions
EP0941384B1 (de
Inventor
Michael James Jaycock
Martin Derek Phillipson
Claes Zetter
Tapio Vihervaara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Raisio Chemicals UK Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Raisio Chemicals UK Ltd filed Critical Raisio Chemicals UK Ltd
Publication of EP0941384A1 publication Critical patent/EP0941384A1/de
Application granted granted Critical
Publication of EP0941384B1 publication Critical patent/EP0941384B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16Sizing or water-repelling agents
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/28Starch
    • D21H17/29Starch cationic
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/62Rosin; Derivatives thereof
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63Inorganic compounds
    • D21H17/66Salts, e.g. alums

Definitions

  • the present invention relates to a "one-shot" rosin emulsion incorporating a cationic starch derivative for use in paper sizing and also relates to a method of paper sizing using the one-shot composition.
  • a rosin emulsion and a soluble aluminium salt such as aluminium sulphate
  • aluminium sulphate e.g. in the form of paper- makers alum [Al 2 (S0 4 ) 3 .16-18H 2 O], aluminium chloride, poly-aluminium chloride or aluminium chlorohydrate.
  • emulsion is conventionally used to describe the rosin product it should more properly be called a dispersion since although made as an emulsion, the particles are effectively solid at ambient temperature).
  • the rosin emulsion and aluminium salt are generally used as separate additions to the paper making process.
  • One-shot composition may be produced by vigorous stirring of an anionic Bewoid rosin emulsion (e.g. stabilised with casein) and an aluminium salt such that agitation is continued beyond formation of an initial precipitate to convert the latter into a cationic emulsion. Production of such emulsions using this technique is disclosed in GB-A-2 050 453.
  • Cationic emulsions made by this type of technique are not in very common use although there are a few which are still on the market.
  • a limitation of such cationic emulsions is that often they are not as stable as the anionic rosin emulsions from which they are derived, and obtaining reproducibility is not always easy. It has therefore been the practice to include a cationic stabiliser as one component of the emulsion formed from the anionic Bewoid emulsion and the aluminium salt.
  • cationic stabilisers include quatemised and other cationised starches.
  • a "one-shot" composition for use in paper sizing comprising an admixture of a rosin emulsion, a soluble aluminium salt and a cationic starch derivative which has a charged state of 0.5 to 5.0 m equivalents per gramme and which has been produced by a process in which the starch structure was split prior to the cationising step.
  • composition of the invention thus incorporates a cationic polymer derived from a degraded starch and having a charge density (i.e. the average number of milli- equivalents of cationised atoms per gramme of polymer) of 0.5 to 50.
  • a charge density i.e. the average number of milli- equivalents of cationised atoms per gramme of polymer
  • charge density i.e. the average number of milli- equivalents of cationised atoms per gramme of polymer
  • the low viscosity and higher charge of the cationic polymer permits the charge of an anionic rosin emulsion to be reversed at low concentrations of the cationic polymer to produce a useable cationic emulsion and to produce a range of cationicities that may be tailored to meet specific demands of a mill.
  • the cationic polymer has a charge density of 0.5 to 4.5 and more preferably 1 to 3.5 m equivalents per gramme.
  • Cationic polymers produced from degraded starch for use in the invention may be produced with a range of molar masses and degree of cationisation. Furthermore, it is possible for solutions of such polymers to be produced containing up to 55% by weight of the polymer without being excessively viscous. Therefore it is possible in accordance with the invention to produce a range of "one-shot" cationic compositions which have sufficient cationicity for a particular application without being too viscous.
  • the cationic polymer employed in the invention is a quatemised derivative of a degraded starch.
  • a derivative has a degree of substitution of at least 0.15, more preferably 0.15 to 1.30 and even more preferably 0.20 to 1.10 quaternary groups per glucose unit. Ideally this degree of substitution is 0.20 to 0.80 and most preferably 0.50 to 0.80.
  • the cationic polymers used in the present invention may be produced by treating starch with an agent which will partially "fragment" the polysaccharide chain (e.g. by use of an oxidising agent such as hydrogen peroxide) and subsequently cationising the "fragmented" product in a reaction in which the solids content is a minimum of 50% (more preferably at least 55%) by weight.
  • the cationizing agent may be used in an amount of 20 to 160%, most preferably 80 to 120%, by weight of the amount of degraded starch thereby allowing the degree of cationization to be readily controlled.
  • the preferred quaternising chemical is 2,3-epoxypropyl trimethyl ammonium chloride although other cationizing agents may be used.
  • Preferred cationic polymers for use in the invention have a nitrogen content in the range of approximately 1-5% (for the cationizing chemical being 2,3- epoxypropylene trimethyl ammonium chloride). It is particularly preferred that cationic, oxidised starch derivatives for use in the invention have a nitrogen content of 3-5%, more preferably 3-4%, and ideally about 3.5% (for the cationizing chemical being 2,3-epoxypropylene trimethyl ammonium chloride).
  • the cationic polymer for use in the invention has a molecular weight in the range of 100,000 to 500,000 Daltons, more preferably 150,000 to 450,000.
  • Particularly suitable quatemised, oxidised starch derivatives for use in formulating the emulsions of the invention are available under the trade mark RAIFIX which designates a range of products of varying cationicity and molecular weight.
  • Typical RAIFIX products have a degree of substitution (by the cationizing agent) of 0.1 to 1.1 which corresponds to a nitrogen content in the range of approximately 1-5% (for the cationizing chemical being 2,3-epoxypropylene trimethyl ammonium chloride).
  • RAIFIX products are available under the following five figure product codes:
  • the first three figures are representative of molecular weight (the higher the number the higher the percentage molecular weight) and the final two figures being approximately ten times the nitrogen content.
  • Estimates of the relative molar mass of the RAIFIX products are 100,000 Daltons for the OlOxx designations and 500,000 Daltons for the 250xx designations.
  • the rosin used in the emulsion of the invention may be for example be a wood rosin, gum rosin, tall oil rosin or mixtures thereof.
  • the rosin may be maleated, fortified, unfortified, hydrogenated or disproportionated.
  • the rosin may optionally be esterified. If a tall oil rosin is used then it is preferred that it be pre-treated with paraformaldehyde.
  • the preferred rosin for use in the invention is a maleated or fumarated rosin.
  • the rosin may be compounded with tall oil fatty acids as proposed in UK-A-2 268 941.
  • Tall oil fatty acids are available for example under the designation CENTURY MO6 (ex Union Camp Chemicals Limited). Any other rosin diluent (e.g. a hydrocarbon resin) may alternatively be used.
  • the rosin emulsion from which the "one-shot" composition is produced may, for example, have a solids content of 30 to 50% by weight.
  • This emulsion may be of a rosin which has been fortified with maleic anhydride or fumaric acid.
  • the emulsion may be an anionic rosin emulsion, e.g. a casein stabilised Bewoid rosin emulsion. It is however also within the scope of the invention that the rosin emulsion (from which the one-shot composition is produced) be a cationic rosin emulsion (e.g. as described in EP-A-0 406 461).
  • the aluminium salt may, for example, be aluminium sulphate (e.g. paper makers alum), aluminium chloride, polyaluminium chloride or aluminium chlorohydrate.
  • the starch derivative is, as indicated, preferably a product as available under the trade mark RAIFIX.
  • the "one-shot" composition will generally have a solids content of at least 10% more usually at least 20%. Typically the solids content will be in the range 20% to 35%o, e.g. 27% to 34% by weight.
  • the "one shot” composition will be formulated so that the relative amounts of rosin, aluminium salt and starch derivative are in the ratio range 1 :(1-1.5, e.g. ca l.4):(0.1-0.5, e.g. ca ⁇ .3).
  • compositions in accordance with the invention may be produced by admixture of the various components followed by homogenisation to produce a smooth, low viscosity emulsion (preferably by initial mixing of rosin and starch derivatives prior to mixing of the aluminium salt).
  • One-shot compositions in accordance with the invention may be used for the sizing of paper and therefore according to a second aspect of the present invention there is provided a method of producing paper in which sizing of the fibres of the paper is effected using a "one-shot" composition in accordance with the first aspect of the invention.
  • the one-shot composition may be added at the wet-end of the paper making process (i.e. to a dispersion of the paper making fibres before the dispersion is laid onto the paper making wire machine or at a size press after formation of the paper web.
  • the amount of composition used for sizing the paper will typically be such that the amount of rosin is 0.2-3% dry basis on the weight of fibres.
  • the invention is illustrated by the following non-limiting Example.
  • Formulations A-G as identified in Table 1 were produced from the rosin emulsion identified under (1) below, at least one of the aluminium salts identified under (2), and one of the starch derivatives identified under (3).
  • the rosin emulsion used was that available under the trade mark NEUSIZE 3 from Roe Lee Paper Chemicals Co. It is a fortified gum rosin emulsion, with casein as a stabiliser, at 30%) solids by weight.
  • the aluminium compound used was at least one of
  • the starch derivative used was one of
  • All formulations (i.e. A-G) were produced by mixing the identified components in the order indicated with a laboratory stirrer and then passing the resultant suspension through a Christisen Scientific Equipment Ltd, H5000, air powered microfluidiser to produce a smooth, low viscosity emulsion.
  • the mean particle size of the resultant emulsion and its stability are shown in Table 1. Certain of the formulations were tested for their sizing properties. For this purpose, the 1 minute Cobb value was obtained for the 10th sheet in a series made with recycled backwater. This technique has been shown in other investigations to give results nearer those obtained on a full scale paper machine than single hand sheet results.
  • the furnish used was a mixed hardwood, softwood furnish containing 70% birch and 30% bleached craft softwood.
  • NEUSIZE 3 For comparison of the efficiency of the tested formulations, a similar test was conducted using NEUSIZE 3 and paper makers alum had a similar level of rosin addition and this resulted in a Cobb value of 20.8. During all of these experiments, a poly-acrylamide (Percol 63) was added at a rate of 300g per tonne.
  • formulation B was a stable product which gave a similar Cobb value to the comparative sizing test using NEUSIZE 3 and paper makers alum.
  • Formulation B is therefore the preferred formulation of Table 1.
  • Formulation A was susceptible to thickening and separation whereas Formulation B was perfectly stable.
  • Formulations E and F also displayed some thixotropy but this could be controlled by changing the amount and type of RAIFIX. Table 1. Formulations of various one-shot emulsions and their properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP97947760A 1996-11-30 1997-12-01 Stärkederivat enthaltende kolophoniumemulsion zur papierleimung Expired - Lifetime EP0941384B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9625006 1996-11-30
GBGB9625006.3A GB9625006D0 (en) 1996-11-30 1996-11-30 'One-shot'rosin emulsion including starch derivative for paper sizing
PCT/GB1997/003197 WO1998024972A1 (en) 1996-11-30 1997-12-01 Rosin emulsion including starch derivative for paper sizing

Publications (2)

Publication Number Publication Date
EP0941384A1 true EP0941384A1 (de) 1999-09-15
EP0941384B1 EP0941384B1 (de) 2004-03-24

Family

ID=10803790

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97947760A Expired - Lifetime EP0941384B1 (de) 1996-11-30 1997-12-01 Stärkederivat enthaltende kolophoniumemulsion zur papierleimung

Country Status (11)

Country Link
US (1) US6290765B1 (de)
EP (1) EP0941384B1 (de)
AT (1) ATE262616T1 (de)
AU (1) AU5400998A (de)
CA (1) CA2273213C (de)
DE (1) DE69728285T2 (de)
ES (1) ES2218704T3 (de)
FI (1) FI117678B (de)
GB (1) GB9625006D0 (de)
PT (1) PT941384E (de)
WO (1) WO1998024972A1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9721188D0 (en) * 1997-10-08 1997-12-03 Raisio Chemicals Uk Limited Rosin emulsion
FI107173B (fi) * 1998-07-10 2001-06-15 Raisio Chem Oy Paperinvalmistuksen lisäaine
US6716313B2 (en) 1998-07-10 2004-04-06 Raisio Chemicals, Ltd. Additive for paper making
AU1099901A (en) 1999-10-20 2001-04-30 Grain Processing Corporation Compositions including reduced malto-oligosaccharide preserving agents, and methods for preserving a material
FI113968B (fi) * 2001-05-23 2004-07-15 Raisio Chem Oy Kationisella polysakkaridilla stabiloitu liuospolymeeri
US6911114B2 (en) 2002-10-01 2005-06-28 Kimberly-Clark Worldwide, Inc. Tissue with semi-synthetic cationic polymer
MX2009009394A (es) 2007-03-15 2009-09-11 Basf Se Composiciones de revestimiento sensibles al calor a base de derivados de resorcinil triazina.
WO2009024497A1 (en) * 2007-08-22 2009-02-26 Basf Se Laser-sensitive coating composition
CA2702732A1 (en) * 2007-11-07 2009-05-14 Basf Se New fiber products
US20120045624A1 (en) 2008-10-27 2012-02-23 Basf Se Aqueous laser-sensitive composition for marking substrates
FR2992967B1 (fr) 2012-07-06 2016-01-22 Roquette Freres Melanges de polyvinylamines et de compositions de matieres amylacees cationiques liquides comme agents ameliorant la resistance a sec des papiers et des cartons

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL259434A (de) * 1959-12-24
GB2050453B (en) * 1979-05-23 1983-02-09 Tenneco Chem Chemical compositions useful in the manufacture of paper sizing agents
SE8405260L (sv) * 1984-10-22 1986-04-23 Eka Ab Hydrofoberingsmedel for organiska fibrer, serskilt cellulosafibrer, sett att framstella detta medel samt anvendningen av medlet for meldhydrofobering
FI94135C (fi) * 1993-12-27 1995-07-25 Raisio Chem Oy Kationisen tärkkelyksen valmistusmenetelmä
SE9501765D0 (sv) * 1995-05-12 1995-05-12 Eka Nobel Ab Sizing dispersions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9824972A1 *

Also Published As

Publication number Publication date
WO1998024972A1 (en) 1998-06-11
DE69728285D1 (de) 2004-04-29
ATE262616T1 (de) 2004-04-15
US6290765B1 (en) 2001-09-18
FI974372A (fi) 1998-05-31
AU5400998A (en) 1998-06-29
DE69728285T2 (de) 2005-03-10
CA2273213A1 (en) 1998-06-11
GB9625006D0 (en) 1997-01-15
CA2273213C (en) 2006-08-22
ES2218704T3 (es) 2004-11-16
PT941384E (pt) 2004-08-31
FI974372A0 (fi) 1997-11-28
EP0941384B1 (de) 2004-03-24
FI117678B (fi) 2007-01-15

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